Niobium and vanadium organometallic precursors for thin film deposition

ABSTRACT

Disclosed are methods for forming a metal-containing layer on a substrate. The methods include providing a vapor and at least one reaction gas and reacting the vapor and the reaction gas with the substrate by a deposition process. The vapor may be selected from the group consisting of (Cp)V(═NtBu)(NEt 2 ) 2 ; (Cp)V(═NtBu)(NMe 2 ) 2 ; (Cp)V(═NtBu)(NEtMe) 2 ; (Cp)V(═NiPr)(NEt 2 ) 2 ; (Cp)V(═NiPr)(NMe 2 ) 2 ; (Cp)V(═NiPr)(NEtMe) 2 ; (Cp)V(═NC 5 H 11 )(NEt 2 ) 2 ; (Cp)V(═NC 5 H 11 )(NMe 2 ) 2 ; (Cp)V(═NC 5 H 11 )(NEtMe) 2 ; (Cp)Nb(═NtBu)(NEt 2 ) 2 ; (Cp)Nb(═NtBu)(NMe 2 ) 2 ; (Cp)Nb(═NtBu)(NEtMe) 2 ; (Cp)Nb(═NiPr)(NEt 2 ) 2 ; (Cp)Nb(═NiPr)(NMe 2 ) 2 ; (Cp)Nb(═NiPr)(NEtMe) 2 ; (Cp)Nb(═NC 5 H 11 )(NEt 2 ) 2 ; (Cp)Nb(═NC 5 H 11 )(NMe 2 ) 2 ; and (Cp)Nb(═NC 5 H 11 )(NEtMe) 2 . The reaction gas may be selected from the group consisting of hydrogen, hydrogen sulfide, hydrogen selenide, hydrogen telluride, carbon monoxide, ammonia, organic amine, silane, disilane, higher silanes, silylamines, diborane, hydrazine, methylhydrazine, chlorosilane, chloropolysilane, metal alkyl, arsine, phosphine, trialkylboron, oxygen, hydrogen peroxide, nitrous oxide, nitrogen monoxide, nitrogen dioxide, alcohols, plasma comprising fragments of those species, and combinations thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation application of U.S. patent application Ser. No.13/123,013, filed Oct. 6, 2009, which is a 371 of International PCTApplication PCT/EP2009/062964, filed Oct. 6, 2009, which claims priorityto EP Application 08305649.9, filed Oct. 7, 2008, the entire contentsare incorporated herein by reference.

SUMMARY

The invention relates to a new class of chemical compounds and their usein metal containing film deposition.

BACKGROUND

The continuous shrink of the critical sizes in modern Integrated Circuit(IC) features associated with 3D topology architectures offers highestdensity at the expense of process complexity.

According to the International Technology Roadmap for Semiconductors(ITRS), physical techniques commonly used in the semiconductor industryfor the deposition of thin films are no more suitable to meet therequirements in the future technology node, notably for high aspectratio structures. Techniques like PVD (Physical Vapor Deposition), i-PVD(ionized-Physical Vapor Deposition) or PECVD (Plasma-Enhanced ChemicalVapor Deposition), employing high energy particles, induce high stickingcoefficient which leads to poor step coverage, especially along thesidewalls.

The main industrial options to enable the deposition of highly uniformand conformal thin films with reasonable throughput in high aspect ratiostructures are techniques such as MOCVD (Metal-Organic Chemical VaporDeposition) or ALD (Atomic Layer Deposition).

However, films deposited by MOCVD need high thermal budget and generallyfollow a 3D-growth mechanism described by a Volmer-Weber model. Thinfilms grow by clusters nucleation and such technique leads toinsufficient step coverage.

The typical ALD process (e.g as described in RITALA M., LESKELA M.,Atomic Layer Deposition, Handbook of thin films materials) involvesgaseous reactants led onto a substrate by pulses, separated by inert gaspurging. In MOCVD, gaseous reactants are injected simultaneously andreact by thermal self-decomposition while in ALD; the loss of the ligandis thermally induced by reaction with the surface groups on thesubstrate. In a temperature range, the surface reactions areself-limited, which allow the deposition of highly uniform and conformalfilms. Precursors must be volatile and stable enough to be easilytransferred to the reaction chamber without being decomposed.

Moreover, they must be reactive enough with the chemical groups of thesurface to ensure reasonable growth rate.

ALD is of particular interest for the deposition of group V (V, Nb, Ta)metal containing films. Today, there still exist the needs for metalorganic precursors in liquid state at room temperature (or close to roomtemperature) having a high volatility and having a high versatility:suitable for various applications in the semi-conductor manufacture.Interest for conductive (resistivity <1000 μΩ·cm) group V (V, Nb, Ta)metal containing thin films deposited by ALD has risen in the past fewyears for several main applications such as: copper diffusion barrier inBEOL applications, CMOS metal gate, electrodes for Metal-Insulator-Metalapplications (DRAM . . . ), and/or the like in TFT-LCD applications.

Group V (V, Nb, Ta) metal containing films are also of particularinterest for High-k layers in memory devices

Halides such as CpNbCl₄ (CAS 33114-1507), NbF₅, NbBr₅ (Thin solid films,1981, 79, 75), NbCl₅ (Crystal growth, 1978, 45, 37) and such as TaCl₅,disclosed in U.S. Pat. No. 6,268,288, have been widely investigated.However, some by-products generated during the deposition process, suchas HCl or Cl₂, can cause surface/interface roughness that can bedetrimental to the final properties. Moreover, Cl or F impurities can bedetrimental to the final electrical properties. It is therefore expectedto find new compounds having sufficient volatility but withoutcontaining Cl, F, or Br atoms.

Many Group V precursors have been considered to enable such deposition.Examples can be given as follows:

Alkoxides such as penta-ethoxy-Tantalum (PET) are widely used anddescribed. However, they lead to oxygen containing films and are notsuitable for the deposition of metal containing films which are used inparticular as electrodes and which should not contain oxygen even attrace level. The same problem is observed for compounds such asCp₂Nb(H)(CO), CpNb(CO)₄ (J. Organomet. Chem 557(1998)77-92), V(CO)₆(Thermochimica Acta, 1984, 75, 71), (η⁵-C₅H₅)V(CO)₄ (M. L. Green, R. A.Levy, J. Metals 37 (1985) 63).

U.S. Pat. No. 6,379,748 discloses an improvement to PET. Alkyl bondshave been introduced, e.g. by using TaMe₃(OEt)₂ instead of Ta(OEt)₅(PET). Volatility was thereby significantly improved without affectingthe melting point.

However, TaMe₃(OEt)₂ does not allow versatile deposition: in particular,oxygen free metal cannot be obtained.

U.S. Pat. No. 6,368,398 discloses another improvement with the use forinstance of Ta[OC(O)C(CH₃)₃]₅, however with the same limitation asdisclosed here above.

WO 02/20870 discloses the use of tert-butylimido(tris(diethylamido)Tantalum, TBTDET, for the deposition of Ta₂O₅.

U.S. Pat. No. 6,593,484, US 2004/0219784 disclose a method of depositionof Tantalum nitride films by sequential injection of TBTDET or TAIMATAand other N source.

U.S. Pat. No. 6,379,748 discloses Ta(Me₃SiCp)₂H₃, which is abiscyclopentadienyl Ta hydride which is a solid having a low volatility.

BRIEF DESCRIPTION OF THE DRAWINGS

For a further understanding of the nature and objects for the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying drawing,wherein:

FIG. 1 shows a structure of a compound having the formulaCp(R¹)_(m)M(NR² ₂)₂(═NR³) (I) according to the invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The invention includes both methods and compounds to achieve the desiredresults, as described, but is not limited to the various embodimentsdisclosed.

According to a first embodiment, the invention relates to a compound ofthe formula Cp(R¹)_(m)M(NR² ₂)₂(═NR³) (I):

Wherein:

M is a metal independently selected from Vanadium (V) or Niobium (Nb)and m≦5;

R¹ is an organic ligand, each one independently selected in the groupconsisting of H, linear or branched hydrocarbyl radical comprising from1 to 6 carbon atom;

R² is an organic ligand, each one independently selected in the groupconsisting of H, linear or branched hydrocarbyl radical comprising from1 to 6 carbon atom;

R³ is an organic ligand selected in the group consisting of H, linear orbranched hydrocarbyl radical comprising from 1 to 6 carbon atom.

Alternatively, R¹ is an organic ligand, each one independently selectedin the group consisting of H, linear or branched; alkyl, alkylsilyl,alkylamides, alkylsilylamides and/or alkoxides. R² may be chosen betweenan alkyl, alkylsilyl, alkylamides, alkylsilylamides and/or alkoxides. R³may be chosen between an alkyl, alkylsilyl, alkylamides,alkylsilylamides and/or alkoxides, preferably, R³ is an alkyl with 3 or4 carbon atoms such as isopropyl or tert-butyl.

In a specific configuration, each R¹ and R² is different from oneanother, which can have beneficial features on the compound physicalproperties.

Alternatively, R¹ is selected in the group consisting of H, an alkylcomprising from 1 to 4 carbon atom, preferably, R¹ is H or methyl orethyl or isopropyl or tert-butyl;

R² is an alkyl comprising from 1 to 3 carbon atom, more preferably, R²is an alkyl with 1 or 2 carbon atom; and

R³ is alkyl with 3 or 4 carbon atoms; more preferably, R³ is isopropylor tert-butyl.

According to other embodiments, the invention relates to:

-   -   A compound, wherein each R¹ are different from one another and        each R² are different from one another.    -   A compound, wherein m=0 in the formula (I).    -   The compounds:        -   (Cp)V(═NtBu)(NEt₂)₂        -   (Cp)V(═NtBu)(NMe₂)₂        -   (Cp)V(═NtBu)(N(EtMe)₂        -   (Cp)V(═NiPr)(NEt₂)₂        -   (Cp)V(═NiPr)(NMe₂)₂        -   (Cp)V(═NiPr)(NEtMe)₂        -   (Cp)V(═NC₅H₁₁)(NEt₂)₂        -   (Cp)V(═NC₅H₁₁)(NMe₂)₂        -   (Cp)V(═NC₅H₁₁)(NEtMe)₂        -   (Cp)Nb(═NtBu)(NEt₂)₂        -   (Cp)Nb(═NtBu)(NMe₂)₂        -   (Cp)Nb(═NtBu)(N(EtMe)₂        -   (Cp)Nb(═NiPr)(NEt₂)₂        -   (Cp)Nb(═NiPr)(NMe₂)₂        -   (Cp)Nb(═NiPr)(NEtMe)₂        -   (Cp)Nb(═NC₅H₁₁)(NEt₂)₂        -   (Cp)Nb(═NC₅H₁₁)(NMe₂)₂        -   (Cp)Nb(═NC₅H₁₁)(NEtMe)₂

According to another embodiment, the invention relates to a method forforming a metal-containing layer on a substrate, the method comprisingat least the steps of:

a) providing a vapor comprising at least one precursor compound of theformula (I);

b) reacting the vapor comprising the at least one compound of formula(I) with the substrate, according to a deposition process, to form alayer of a metal-containing complex on at least one surface of saidsubstrate.

According to other embodiments, the invention relates to:

-   -   A method, wherein the said deposition process is an atomic layer        deposition process.    -   A method, wherein the said deposition process is a chemical        vapor deposition process.    -   A method, further comprising the step:

c) reaction of the complex obtained in step b) with a reagent selectedfrom another metal source, reducing reactants and/or nitriding reactantsand/or oxidizing reactants.

-   -   A method, wherein the vapour provided in step a) further        comprises one or more metal (M′)-organic precursor(s) to produce        thin films containing M and M′.    -   A method, further comprising providing at least one reaction gas        wherein the at least one reaction gas is selected from the group        consisting of hydrogen, hydrogen sulfide, hydrogen selenide,        hydrogen telluride, carbon monoxide, ammonia, organic amine,        silane, disilane, higher silanes, silylamines, diborane,        hydrazine, methylhydrazine, chlorosilane and chloropolysilane,        metal alkyl, arsine, phosphine, trialkylboron, oxygen, ozone,        water, hydrogen peroxide, nitrous oxide, nitrogen monoxide,        nitrogen dioxide, alcohols, plasma comprising fragments of those        species, and combinations thereof, preferably ozone or water.    -   A method, wherein the temperature of the substrate is 100° C. to        700° C., preferably 150° C. to 450° C., and wherein the        deposition chamber containing the substrate has a pressure of        1.33 Pa (=0.01 Torr) to 100 kPa (=800 Torr), preferably below 25        kPa (=200 Torr).    -   A method, further comprising the step of purging excess vapor        comprising the at least one compound of formula (I) from the        substrate, with an inert gas selected from the group consisting        of hydrogen, nitrogen, helium, argon, and mixtures thereof.    -   A method, wherein the metal-containing layer has a thickness of        more than 0 μm to 10 μm.    -   A method of manufacturing a semiconductor structure, comprising        the steps of the method defined above, wherein the substrate is        a semiconductor substrate.        Related Techniques for the Deposition of Vanadium (V) or Niobium        (Nb) Containing Films

The vaporization of the metal source is realized by introducing acarrier gas into a heated container containing the said metal source.The container is preferably heated at a temperature allowing to get thesaid metal source at a sufficient vapor pressure. The carrier gas can beselected from Ar, He, H₂, N₂ or mixtures of them. The said metal sourcecan be mixed to a solvant or to another metal source or to a mixture ofthem in the container. The container can for instance be heated attemperatures in the range of 25° C.-200° C. Those skilled in the artwill consider that the temperature of the container can be adjusted tocontrol the amount of precursor vaporized. To control the evaporationlevel in the container, the pressure in the container can be modified.By reducing the pressure in the container, the level of vaporation ofthe metal source can be increased. The pressure in the container can forinstance be changed in the range of mTorr till 800 Torr.

The said metal source can also be fed in liquid state to a vaporizerwhere it is vaporized. The said metal source can be mixed to a solvent.The said metal source can be mixed to another metal source. The saidmixture of metal sources can be mixed to a solvent or a mixture ofsolvent. The said metal source can be mixed to a stabilizer. The saidsolvent can be selected in the group consisting of alcanes such ashexane, heptane, octane, aromatic solvents such as benzene, toluene,mesitylene, xylene, silicon containing solvent such ashexamethyldisiloxane, hexamethyldisilazane, tetramethylsilane, sulphurcontaining solvents such as dimethylsulfoxide, oxygen containing solventsuch as tetrahydrofuran, dioxane.

The said vaporized metal source is then introduced into a reactionchamber where it is contacted to the surface of a substrate. Thesubstrate can be heated to sufficient temperature to obtain the desiredfilm at sufficient growth rate and with desired physical state andcomposition. Typical temperatures range from 100° C. to 700° C.Preferably the temperature is lower or equal to 450° C. The process canbe assisted by a plasma technique, chosen without limitation, to improvethe reactivity of the said vaporized metal source and/or the reactivityof other gaseous species, used in the process.

In one embodiment, the process of the invention consists in introducingsimultaneously a Vanadium (V) or Niobium (Nb) metal-organic precursordescribed by the general formula Cp(R¹)_(m)M(NR² ₂)₂(═NR³) into areaction chamber with or without a reagent. The said metal-organicprecursor reacts by thermal self-decomposition with the surface of asubstrate. The reagent is selected from reducing reactants, nitridingreactants, oxidizing reactants, or a mixture of them.

In one embodiment, the process of the invention consists in introducingsimultaneously a Vanadium (V) or Niobium (Nb) metal-organic precursordescribed by the general formula Cp(R¹)_(m)M(NR² ₂)₂(═NR³) into areaction chamber with or without a reagent and another metal source,being independently selected from any other element in the group II,III-A, III-B, Sulpher (S), tantalum (Ta), transition metal, lanthanoids,or rare-earth metals. The said metal-organic precursors react by thermalself-decomposition with the surface of a substrate. The reagent isselected from reducing reactants, nitriding reactants, oxidizingreactants, or a mixture of them.

In one embodiment, the process of the invention consists in introducingalternatively a Vanadium (V) or Niobium (Nb) metal-organic precursordescribed by the general formula Cp(R¹)_(m)M(NR² ₂)₂(═NR³) into areaction chamber with a reagent. In a temperature range, the saidmetal-organic precursor reacts in a self-limited manner with the bondspresent onto the surface of a substrate. Preferably, un-depositedmetal-organic precursors molecules are removed from the reactionchamber. The reagent introduced, reacts also in a self-limited manner.Once all the complexes present on the surface of the substrate havereacted with the reagent, species are removed from the reaction chamberby a purge gas. The purge gas can for instance be selected within N₂,Ar, He, H₂ or mixtures of them. The purge gas may additionally containother gas species that do not modify the chemical reactivity of thesurface. Alternatively, the purge can be realized by vacuum. Thisprocess can be repeated as many times as necessary to reach the desiredfilm thickness. The reagent is selected from reducing reactants,nitriding reactants, oxidizing reactants, or a mixture of them.

In one embodiment, the process of the invention consists in introducingalternatively first a Vanadium (V) or Niobium (Nb) metal-organicprecursor described by the general formula Cp(R¹)_(m)M(NR² ₂)₂(═NR³)into a reaction chamber and second a reagent or another metal source,being independently selected from any other element in the group II,III-A, III-B, Sulphur (S), tantalum (Ta), transition metal, lanthanoids,or rare-earth metals. In a temperature range, the said metal-organicprecursors react in a self-limited manner with the bonds present ontothe surface of a substrate. Preferably, un-deposited metal-organicprecursors molecules are removed from the reaction chamber. The reagentintroduced, reacts also in a self-limited manner. Once all the complexespresent on the surface of the substrate have reacted with the reagent,species are removed from the reaction chamber by a purge gas. The purgegas can for instance be selected within N₂, Ar, He, H₂ or mixtures ofthem. The purge gas may additionally contain other gas species that donot modify the chemical reactivity of the surface. Alternatively, thepurge can be realized by vacuum. This process can be repeated as manytimes as necessary to reach the desired film thickness. The reagent isselected from reducing reactants, nitriding reactants, oxidizingreactants, or a mixture of them.

The compounds of the formula (I) or in admixture, are used to depositefilms of various compositions (as disclosed herein after) using anywell-known deposition method using vapor phase deposition, such as MOCVD(Metal Organic Chemical Vapor Deposition), ALD (Atomic LayerDeposition), PE-ALD (Plasma Enhanced Atomic Layer Deposition) and anyother deposition method such as PECVD (Plasma Enhanced Chemical VaporDeposition) or as pulsed CVD.

These new group V metal precursors are thus useful for pure metal,metallic oxide, oxynitride, nitride and/or silicide film deposition tomake electrodes and/or high k layers, and/or copper diffusion barrierlayers and the like.

In the ALD process the preferred temperature is in the range of 100° C.to 450° C., more preferably 150° C. to 350° C., the preferred pulseduration in ALD is one second, the preferred pressure is in the range of0.01 Torr to 800 Torr, more preferably from 0.1 Torr to 200 Torr. andthe preferred carrier gas is selected from N₂, He, Ar, H₂, morepreferably Ar or N₂. The preferred N₂ canister flow is in the 30-200sccm range, preferably 50 sccm to 100 sccm

In the CVD process, the preferred temperature is in the range of 100° C.to 700° C., more preferably from 200° C. to 500° C., the preferredpressure is in the range of 0.01 Torr to 800 Torr, preferably from 1Torr to 200 Torr and the preferred carrier gas is selected from N₂, He,Ar, H₂, more preferably Ar or N₂. The preferred N₂ canister flow is inthe 30-200 sccm range, preferably 50 sccm to 100 sccm.

In the PECVD process, the preferred temperature is in the range of 100°C. to 700° C., more preferably from 100° C. to 500° C., the preferredpressure is in the range of 0.01 Torr to 800 Torr, preferably from 1Torr to 200 Torr, the preferred carrier gas is selected from N₂, He, Ar,H₂, more preferably Ar or N₂ and the preferred N₂ canister flow is inthe 30-200 sccm range, preferably 50 sccm to 100 sccm. H or NH radicalsare produced by a remote plasma system and used as co-reactant.

In these above mentioned uses, any of the compound of the formula (I) asdefined above, can be used alone or in admixture with one or severalother compounds of the said formula (I) and/or with any appropriateadditive which useful when depositing a metal containing film asprovided hereafter. According to a particular embodiment the inventionrelates to a use as defined above of such an admixture having a meltingpoint lower than or equal to about 50° C. and more preferably lower thanor equal to 35° C., i.e. shall be in liquid form or close to liquid format room temperature, which makes their delivery easier, and or having avapor pressure higher than 0.01 Torr at 100° C.

Various films can be obtained on a substrate by using the precursorsdescribed here above, such as nitrides, carbides, silicides,nitro-silicides (MSiN), oxydes (e.g. MeO_(j)), oxynitrides (MO_(x)N_(y))and oxynitrides from two different metals M¹ and M² (M¹M²O_(x)N_(y)).

The process according to the invention may be summarized as shown in theFIG.

In accordance with one embodiment, the vaporization of the new metalsource is realized by introducing a carrier gas into a heated containercontaining the said new metal source. The container is preferably heatedat a temperature allowing to get the said metal source at a sufficientvapor pressure. The carrier gas can be selected, without limitation,from Ar, He, H₂, N₂ or mixtures of them. The said metal source can bemixted to a solvant or to another metal source or to a mixture of themin the container. The container can for instance be heated attemperatures in the range of 80° C.-140° C. Those skilled in the artwill consider that the temperature of the container can be adjusted tocontrol the amount of precursor vaporized.

In accordance with another embodiment, the said metal source is fed inliquid state to a vaporizer where it is vaporized. The said metal sourcecan be mixed to a solvent. The said metal source can be mixed to anothermetal source. The said mixture of metal sources can be mixed to asolvent or a mixture of solvent. The said metal source can be mixed to astabilizer.

The vaporized metal source is there after introduced into a reactionchamber where it is contacted to a substrate. The substrate can beheated to a sufficient temperature to obtain the desired film atsufficient growth rate and with desired physical state and composition.Typical temperature range from 100° C. to 700° C. Preferably thetemperature is lower or equal to 450° C. The pressure in the reactionchamber is controlled to obtain the desired metal containing film atsufficient growth rate. Typical pressure range from 1.33 Pa (=0.01 Torr)to 13.3 kPa (=100 Torr) or higher.

According to another embodiment, it is possible to mix the metal sourceto a reactant species prior to the introduction of the mixture into thereaction chamber.

In another embodiment of the invention, the metal source may be mixed toa reactant species in the reaction chamber.

According to a further embodiment, the metal source and the reactantspecies are introduced simultaneously (chemical vapor deposition),sequentially (atomic layer deposition) or any combination thereof (oneexample is to introduce the metal source and the other metal sourcetogether in one pulse and oxygen in a separate pulse [modified atomiclayer deposition]; another example is to introduce oxygen continuouslyand to introduce the metal sources by pulse (pulsed-chemical vapordeposition)).

It is also possible to introduce the reactant species into a plasmasystem localized remotely from the reaction chamber to decompose thesespecies into radicals before their introduction into the reactionchamber.

According to a further embodiment, wherein the targeted metal based filmcontains oxygen, such as for example, without limitation metal, oxide ormetal oxy-nitride, the reactant species shall include an oxygen sourcewhich is selected from the group comprising oxygen (O₂), oxygen radicals(for instance O^(•) or OH^(•)), for instance generated by a remoteplasma, ozone (O₃), NO, N₂O, NO₂, moisture (H₂O) and H₂O₂ or any mixturethereof;

According to still a further embodiment, wherein the targeted metalbased film contains nitrogen, such as for example metal nitride or metalcarbo-nitride, the reactant species include a nitrogen source which isselected from, but not limited to, nitrogen (N₂), ammonia, hydrazine andalkyl derivatives, N-containing radicals (for instance N, NH, NH₂ ^(•)),NO, N₂O, NO₂, amines.

If the targeted metal based film contains carbon, such as for examplewithout limitation metal carbide or metal carbo-nitride, the reactantspecies include a carbon source which is selected from, but not limitedto, methane, ethane, propane, butane, ethylene, propylene, t-butylene,isobutylene, CCl₄.

If the targeted metal based film contains silicon, such as for examplemetal silicide, silico-nitride, silicate, silico-carbo-nitride, thereactant species shall include a silicon source which is selected fromthe group comprising SiH₄, Si₂H₆, Si₃H₈, TriDMAS, BDMAS, BDEAS, TDEAS,TDMAS, TEMAS, (SiH₃)₃N, (SiH₃)₂O, trisilylamine, disiloxane,trisilylamine, disilane, trisilane, a alkoxysilane SiH_(x)(OR¹)_(4-x), asilanol Si(OH)_(x)(OR¹)_(4-x) (preferably Si(OH)(OR¹)₃; more preferablySi(OH)(OtBu)₃ an aminosilane SiH_(x)(NR¹R²)_(4-x) (where x is comprisedbetween 0 and 4; R¹ and R² are independently H or a C1-C6 carbon chain,either linear, branched or cyclic; preferably TriDMAS SiH(NMe₂)₃, BTBASSiH₂(NHtBu)₂); BDEAS SiH₂(NEt₂)₂) and mixtures thereof. The targetedfilm can alternatively contain Germanium. The above-mentioned Sicontaining sources, may be replaced by similar Ge containing sources.

It is quite possible to mix a metal source to another metal source todeposit a multi-metal containing film, prior to their introduction intothe reaction chamber or to simultaneously introduce into the reactionchamber, these metal sources and mix them together and/or with otherreactant species in the reaction chamber.

But it is also possible to introduce the first metal source, the secondmetal source and the reactant species in the reaction chambersimultaneously (chemical vapor deposition), sequentially (atomic layerdeposition) or any combination thereof (one example is to introduce thefirst metal source and the second metal sources together in one pulseand oxygen in a separate pulse [modified atomic layer deposition];another example is to introduce oxygen continuously and to introduce themetal source by pulse (pulsed-chemical vapor deposition)).

The second metal source shall be selected from the group comprisingtantalum, lanthanide and rare-earth metal source (Sc, Y, La, Ce, Pr, Nd,Gd . . . ) source such as rare earth diketonatesLn(—O—C(R¹)—C(R²)—C(R³)—O—)(O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(—O—C(R⁷)—C(R⁸)—C(R⁹)—O—)(where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic), a cyclopentadienyl Ln(R¹Cp)(R²Cp)(R³Cp)(where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic), Ln(NR¹R²)(NR³R⁴)(NR⁵R⁶) and mixturesthereof. The second metal source can alternatively be an aluminumsource, selected from the group consisting of trimethyl aluminum,dimethyl aluminum hydride, an alkoxyalane AlR^(i) _(x)(OR′)_(3-x) (wherex is comprised between 0 and 3; R¹ and R² are independently H or a C1-C6carbon chain, either linear, branched or cyclic; preferably AlR¹R²(OR′),most preferably AlMe₂(OiPr)), an amidoalane AlR^(i) _(x)(NR′R″)_(3-x)(where x is comprised between 0 and 3; R¹ and R² are independently H ora C1-C6 carbon chain, either linear, branched or cyclic) and mixturesthereof. The other metal source can alternatively be a tungsten,molybdenum source. The other metal source can alternatively be ahafnium, zirconium or titanium source such as M(OR¹)₄ or otheralkoxide-containing metal sources, M(NR¹R²)₄, or adducts containingthese species. The second metal source can alternatively be a divalentmetal source (preferably Mg, Ca, Zn, Sr, Ba) selected from, but notlimited to metal β-diketonates or adducts containing these species.

The reactants can be introduced simultaneously (chemical vapordeposition), sequentially (atomic layer deposition) any combinationthereof.

EXAMPLES 1. CVD Process Using NbCp(═NtBu)(NEtMe)₂ and Ammonia

NbCp(═NtBu)(NEtMe)₂ is stored into a container. The container is heatedat 120° C. and N₂ is used as carrier gas at a flow of 50 sccm. Ammonia(NH₃) is used as nitrogen source. The substrate is heated at 400° C. Theprecursor is simutaneoulsy introduced into the reaction chamber withNH₃. A film of niobium nitride is obtained.

2. ALD Process Using NbCp(═NtBu)(NEtMe)₂ and Ammonia

NbCp(═NtBu)(NEtMe)₂ is stored into a container. The container is heatedat 120° C. and N₂ is used as carrier gas at a flow of 50 sccm. Ammonia(NH₃) is used as nitrogen source. The substrate is heated at 400° C. Theprecursor is sequentially introduced into the reaction chamber with NH₃:during the first step a pulse of NbCp(═NtBu)(NEtMe)₂ is introducedduring 8 seconds, followed by a 13 seconds N₂ purge. A pulse of NH₃ isthen introduced into the reaction chamber during 8 seconds, followed bya 13 seconds N₂ purge. The first step is then done again. 400 cycles areperformed this way. A film of niobium nitride is obtained.

The precursors according to the present invention are suitable forproducing very thin, uniform and conformal thin films in high aspectratio structures with control of the thickness and composition at theatomic level. Those films are highly desirable for applications in thesemiconductor industry either as for example:

a. Copper diffusion barrier in BEOL applications

b. CMOS metal gate

c. Electrodes in Metal-Insulator-Metal structures

d. High-k layer in Metal-Insulator-Metal structures

Examples: NbN_(x), VNx, Nb, V, VOx, NbOx, TaNbN, TaNbO_(x), BiNbO_(x),BiTaNbO_(x).

Despite the precursors look very suitable for applications in thesemiconductor industry, it is not limited to this industry only. V andNb containing layers can be used among other applications to increasewear resistance, catalytic applications, and sensors.

It will be understood that many additional changes in the details,materials, steps and arrangement of parts, which have been hereindescribed in order to explain the nature of the invention, may be madeby those skilled in the art within the principle and scope of theinvention as expressed in the appended claims. Thus, the presentinvention is not intended to be limited to the specific embodiments inthe examples given above.

What is claimed is:
 1. A method for forming a metal-containing layer ona substrate, the method comprising the steps of: a) providing a vaporcomprising at least one precursor compound selected from the groupconsisting of (Cp)V(═NtBu)(NEt₂)₂; (Cp)V(═NtBu)(NMe₂)₂;(Cp)V(═NtBu)(NEtMe)₂; (Cp)V(═NiPr)(NEt₂)₂; (Cp)V(═NiPr)(NMe₂)₂;(Cp)V(═NiPr)(NEtMe)₂; (Cp)V(═NC₅H₁₁)(NEt₂)₂; (Cp)V(═NC₅H₁₁)(NMe₂)₂;(Cp)V(═NC₅H₁₁)(NEtMe)₂; (Cp)Nb(═NtBu)(NEt₂)₂; (Cp)Nb(═NtBu)(NMe₂)₂;(Cp)Nb(═NtBu)(NEtMe)₂; (Cp)Nb(═NiPr)(NEt₂)₂; (Cp)Nb(═NiPr)(NMe₂)₂;(Cp)Nb(═NiPr)(NEtMe)₂; (Cp)Nb(═NC₅H₁₁)(NEt₂)₂; (Cp)Nb(═NC₅H₁₁)(NMe₂)₂;and (Cp)Nb(═NC₅H₁₁)(NEtMe)₂; b) providing at least one reaction gasselected from the group consisting of hydrogen, hydrogen sulfide,hydrogen selenide, hydrogen telluride, carbon monoxide, ammonia, organicamine, silane, disilane, higher silanes, silylamines, diborane,hydrazine, methylhydrazine, chlorosilane, chloropolysilane, metal alkyl,arsine, phosphine, trialkylboron, oxygen, hydrogen peroxide, nitrousoxide, nitrogen monoxide, nitrogen dioxide, alcohols, plasma comprisingfragments of those species, and combinations thereof; and c) reactingthe vapor and the reaction gas with the substrate, according to adeposition process, to form the metal-containing layer on at least onesurface of the substrate.
 2. The method of claim 1, wherein thedeposition process is an atomic layer deposition process.
 3. The methodof claim 1, wherein the deposition process is a chemical vapordeposition process.
 4. The method of claim 1, further comprising thestep: d) reacting the metal-containing layer obtained in step c) with areagent selected from the group consisting of another metal source,reducing reactants, nitriding reactants, oxidizing reactants, andcombinations thereof.
 5. The method of claim 1, wherein the vaporprovided in step a) further comprises at least one precursor compoundcontaining a metal M², and the metal-containing layer formed in step c)contains two metals M¹ and M², wherein M¹ is Vanadium or Niobium.
 6. Themethod of claim 1, wherein a temperature of the substrate is 100° C. to700° C. and wherein the deposition chamber containing the substrate hasa pressure of 1.33 Pa to 100 kPa.
 7. The method of claim 6, wherein thetemperature is 150° C. to 450° C. and the pressure is below 25 kPa. 8.The method of claim 1, further comprising the step of purging excessvapor comprising the at least one precursor compound from the substratewith an inert gas selected from the group consisting of hydrogen,nitrogen, helium, argon, and mixtures thereof.
 9. A method ofmanufacturing a semiconductor structure, comprising the steps of:forming a metal-containing layer on the semiconductor substrate by: a)providing a vapor comprising at least one precursor compound selectedfrom the group consisting of (Cp)V(═NtBu)(NEt₂)₂; (Cp)V(═NtBu)(NMe₂)₂;(Cp)V(═NtBu)(NEtMe)₂; (Cp)V(═NiPr)(NEt₂)₂; (Cp)V(═NiPr)(NMe₂)₂;(Cp)V(═NiPr)(NEtMe)₂; (Cp)V(═NC₅H₁₁)(NEt₂)₂; (Cp)V(═NC₅H₁₁)(NMe₂)₂;(Cp)V(═NC₅H₁₁)(NEtMe)₂; (Cp)Nb(═NtBu)(NEt₂)₂; (Cp)Nb(═NtBu)(NMe₂)₂;(Cp)Nb(═NtBu)(NEtMe)₂; (Cp)Nb(═NiPr)(NEt₂)₂; (Cp)Nb(═NiPr)(NMe₂)₂;(Cp)Nb(═NiPr)(NEtMe)₂; (Cp)Nb(═NC₅H₁₁)(NEt₂)₂; (Cp)Nb(═NC₅H₁₁)(NMe₂)₂;and (Cp)Nb(═NC₅H₁₁)(NEtMe)₂; b) providing at least one reaction gasselected from the group consisting of hydrogen, hydrogen sulfide,hydrogen selenide, hydrogen telluride, carbon monoxide, ammonia, organicamine, silane, disilane, higher silanes, silylamines, diborane,hydrazine, methylhydrazine, chlorosilane, chloropolysilane, metal alkyl,arsine, phosphine, trialkylboron, oxygen, hydrogen peroxide, nitrousoxide, nitrogen monoxide, nitrogen dioxide, alcohols, plasma comprisingfragments of those species, and combinations thereof; and c) reactingthe vapor and the reaction gas with the semiconductor substrate,according to a deposition process, to form the metal-containing layer onat least one surface of the semiconductor substrate.
 10. The method ofclaim 9, wherein the deposition process is an atomic layer depositionprocess.
 11. The method of claim 9, wherein the deposition process is achemical vapor deposition process.
 12. The method of claim 9, furthercomprising the step: d) reacting the metal-containing layer obtained instep c) with a reagent selected from the group consisting of anothermetal source, reducing reactants, nitriding reactants, oxidizingreactants, and combinations thereof.
 13. The method of claim 9, whereinthe vapor provided in step a) further comprises at least one precursorcompound containing a metal M², and the metal-containing layer formed instep c) contains two metals M¹ and M², wherein M¹ is Vanadium orNiobium.
 14. The method of claim 9, further comprising the step ofpurging excess vapor comprising the at least one precursor compound fromthe substrate with an inert gas selected from the group consisting ofhydrogen, nitrogen, helium, argon, and mixtures thereof.
 15. A compoundselected from the group consisting of: (Cp)Nb(═NtBu)(NEt₂)₂(Cp)Nb(═NtBu)(NMe₂)₂ (Cp)Nb(═NtBu)(N(EtMe)₂.
 16. The compound of claim15, wherein the compound is (Cp)Nb(═NtBu)(NEt₂)₂.
 17. The compound ofclaim 15, wherein the compound is (Cp)Nb(═NtBu)(NMe₂)₂.
 18. The compoundof claim 15, wherein the compound is (Cp)Nb(═NtBu)(N(EtMe)₂.